Process for making titanium dioxide



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m *1 m m H m Qmmu w :35 E c QLIIIIIIII Qwmu .53 mmmmu ammqfi amtwmm N5 an mmam m G: 9 NQUW Wm. Q: 8 N Q mmwtqmmkuq m mm? H- JFTORIVEY p 1, 1970 SHEN wu WAN PROCESS FOR MAKING TITANIUM DIOXIDE Filed March 4, 1968 2 Shoots-Sheet L3 MW m R N r m m P M B awe N u u R W W M m 1% T m N m 4 C mdxumm M S W at \s mmfiowwfi 6 53 est 350mm B/ N R m m 1 mn M mm an x a l mwwm mm 5.3 w llhllllll 4 astqmsiu qmmk B mm mm waomuwammmwu mm mm ll :1 ll IT II It w w t n I l llv/wv vm kgmmmm o m G R e at gt mm ha: law he: [m m 8 2st QUEER 29593 7 v v mmmrmwmw mm Gt mm Gt m $23k E mm vw United States Patent Office 3,526,477 Patented Sept. 1, 1970 U.S. Cl. 23-202 6 Claims ABSTRACT OF THE DISCLOSURE In a chlorination process for producing Ti from TiO ore, the temperature in the chlorination stage is maintained within the desired range by recycling thereto chlorine-enriched TiCl A portion of a chlorine containing gas mixture obtained from an oxidation step is directed to a titanium ore chlorination step. The remainder of the gas mixture is directed to a chlorine separation step wherein a portion of the chlorine is recovered as gas and the remainder of the chlorine is absorbed in liquid titanium tetrachloride. The chlorine gas and a portion of the chlorine dissolved in titanium tetrachloride are directed to the chlorination step.

This invention relates to a chlorination process for producing TiO from TiO ore wherein chlorine-enriched TiCl is recycled to an ore chlorination step to maintain the desired temperature therein. More particularly, this invention relates to a chlorination process to produce TiO wherein TiCl is employed to absorb chlorine from by-product gases and the resulting chlorine dissolved in TiCL, is recycled to a TiO ore chlorination step in an amount sufiicient to maintain a desirable temperature therein.

BACKGROUND OF THE INVENTION Titaniferous ore can be converted to pigmentary titanium dioxide by chlorination, to obtain a TiCL; solution which is usually purified, followed by oxidation of the TiCl solution to obtain both pigmentary TiO and a gaseous mixture comprising chlorine, and oxygen. Usually, only a small portion of the gas mixture can be recycled to the initial chlorination unit because the oxygen content thereof causes excessive chlorination temperatures. Thus, in order to recover chlorine for use in the chlorination step, the major portion of the gaseous mixture is treated to separate chlorine from the oxygen by selectively absorbing chlorine in a suitable absorbent, such as liquid TiCl In present processes, the chlorine is stripped from the absorbent and the chlorine gas is recycled to the chlorination stage. Operating in this manner requires relatively large stripping capacity for the overall process which is expensive to operate and maintain. It is desirable to minimize the amount of gas stripped from the TiCl in order to reduce the overall process heating requirements while preventing undesirably high temperatures in the chlorination step.

It is an object of the present invention to provide a process for producing titanium dioxide wherein excess chlorine gas is recycled to a TiO ore chlorination step Without effecting undesirably high temperature therein. It is a further object of the present invention to provide a process for producing titanium dioxide while minimizing needed process stripping capacity. Further objects of the present invention will become evident from the following detailed description.

According to the process of the invention, it has been found that the difliculties of the prior practice can be overcome in a straight-forward and economical manner by selectively absorbing, with TiCl C1 from a gas mixture obtained from a TiCl, oxidation step and thereafter recycling a portion of the chlorine enriched TiCl, to a titanium ore chlorination step. The gas mixture or a portion thereof is directed to a chlorine separation step having an absorption tower, a stripping tower and means for circulating liquid TiCL; between the towers. In the absorption tower, TiCl is countercurrently contacted with a portion of the gas mixture of C1 and 0 obtained from the TlCL; oxidation step. A portion of the chlorine dissolved in TiCl liquid is withdrawn from the absorber and directed to the chlorinator. The remaining chlorine dissolved in TiCL; is circulated to the stripping tower and heated to separate chlorine gas from the TiCl The chlorine gas is recycled to the chlorination stage and the stripped TiCl is cooled and recycled to the absorption tower. Make-up TiCl, is directed to the absorption tower from the chlorination step and/or a purification step for purifying TiCl, obtained from the chlorination step.

The process of this invention provides substantial advantages over the prior art processes. Added amounts of the gas from the oxidation step can be directly introduced into the chlorination unit without risking high reaction temperatures in the chlorination unit since the TiCl and dissolved C1 recycled to the chlorination unit have an endothermic efiect on the chlorination reaction. Thus, the needed stripping capacity and thus the heating requirement, is substantially reduced for the overall process since the C1 enriched T iCl solution is directed to the chlorination stage directly from the absorption step without first being passed through the stripping step. These advantages of this process are obtained While utilizing all the chlorine gas obtained as a by-product in the process.

The amount of chlorine dissolved in TiCl directed to the chlorination unit is sufiicient to maintain the temperature in the chlorination unit in the range of between about 950 C. and about 1050 C., preferably between about 975 C. and about 1025 C. In order to maintain the desired reaction temperature without recycling excessive amounts of TiCl it is desirable to recycle to the chlorination unit less than about 50 volume percent of the gas mixture obtained from the oxidation step. When recycling more than about 50 volume percent of the gas mixture to the chlorination unit the TiCL; which must be recycled to maintain desirable chlorination temperatures becomes undesirably excessive and thereby seriously reduces the rate of Ti0 production for the overall process. This is because the increased amount of TiCl, needed as an endotherm is obtained either directly or indirectly from the TiCL, feed stream to the oxidation step wherein TiO is produced. The amount of chlorine dissolved in TiCl, withdrawn from the absorption tower to maintain the desired chlorination temperature is usually between about 10 and about 25 volume percent of the TiCl circulated between the absorption tower and the stripping tower. The make-up TiCL, supplied to the chlorine separation unit is supplied as either impure TiCl from the chlorination unit or as pure TiCl, from the TiCl purification unit or as a mixture of both streams.

The invention Will be further described with reference to the accompanying drawings, in which FIG. 1 is a flow diagram of the overall process for effecting a titanium-ore chlorination and oxidation, and in which FIG. 2 illustrates, in detail, the manner for utilizing TiCL, to recover chlorine gases from the gas mixture from the TiCl oxidation unit and to recycle the chlorine to the chlorination unit.

Referring now to the FIG. 1, into a chlorination unit 1, there is charged coke flirough feed line 2, a TiO containing ore through feed line 3, a chlorine-containing gas mixture through line 4 from oxidation unit 24, recycle Cl gases through feed line 5, make-up C1 containing gas through feed line 6 and C1 enriched TiCld, from C1 separation unit 33 through feed line 37. The

manner for obtaining recycle C1 containing gas and C1 dissolved in TiCl will be described in detail with reference to FIG. 2. The feed rates of the respective materials to chlorination unit 1 as well as conditions of temperature and pressure therein are maintained to convert the titanium compounds in the ore to TiCl and to convert coke to CO as well as CO A gaseous mixture is recovered from the chlorination unit 1 and directed to cooling step 7 through feed line 8. In cooling step 7, the gaseous metallic compounds including TiCL; are condensed and separated from an uncondensed gas mixture which includes C0, C and HCl. The uncondensed gas mixture is directed through feed line 9 into a water scrubber 10 from which HCl is removed through conduit 11 and into which H O is introduced through line 12. The H O-insoluble CO and CO gases removed from the scrubber 10 through line 13 are directed to an atmospheric flare.

Impure TiCL; is removed from cooling zone 7 through line 35 and directed to TiCl purification unit wherein H impure TiCl is separated from other metallic chloride solids such as ferric chloride and aluminum chloride. The metallic chlorides other than TiCl are removed from purification unit 25 through line 36. The pure TiCl is removed from purification unit 25 through line 26 and treated in a manner hereinafter described.

To the oxidizing zone 24 are added pure TiCl obtained from a purification zone 25 and fed through lines 26 and 39, and oxygen, fed separately through line 27. Reaction conditions maintained in the oxidizing zone 24 are maintained to convert TiCl to TiO The gaseous mixture from oxidizing zone 24 is removed therefrom through line 28 and directed to cooling zone 29. In zone 29, the gas and TiO are cooled to permit collection of pigmentary solids which are separated from uncondensed gases. The TiO is removed from cooling zone 29 through line 30 and recovered.

The uncondensed gaseous mixture issuing from the cooling zone 29 through line 31 comprises C1 and 0 A portion of the mixture is diverted through line 4 and is fed into the chlorination unit 1. The remaining portion of the gas mixture from line 31 is introduced through line 32 into a chlorine separator zone 33. In the chlorine separation zone 33, C1 is absorbed with TiCl obtained either as pure TiCL; from line or as impure TiCl from line 41 or a mixture thereof. The unabsorbed O gases are removed through line 34. Substantially pure chlorine is removed through line 5 and recycled to the chlorination unit 1. Chlorine dissolved in TiCl is removed from C1 separation zone 33 through line 37.

In FIG. 2, the chlorine separation unit 33 referred to in FIG. 1 is shown in greater detail together with the chlorination unit 1, the TiCL; oxidation unit 24 and the TiC1 purification unit 25. The chlorine separation unit 33 comprises an absorber 50, a heat exchanger 51 and a stripper 52. A gas mixture from the TiCl oxidation unit 24 is directed in part through line 4 to chlorination unit 1. The remainder of the gas stream is introduced through line 32 into an absorber tower maintained at a temperature of from l5 C. to C. and a pressure of from to p.s.i.a. The absorber 50 comprises but one section of the overall chlorine separating unit 33 (shown in FIG. 1). Liquid TiCl absorbent is introduced from line 40 and/or 41 and line 42 and 53 into absorber 50 in counterfiow to the gas stream introduced through line 32. In the absorber, C1 is preferentially absorbed by TiCl and the unabsorbed mixture of O is removed from absorbers 50 through line 34. The C1 dissolved in TiCl is removed from absorber 50 through line 54 and a portion thereof is directed through line 37 to the chlorination unit 1.

The remaining chlorine dissolved in TiCl solution stream passes through line 55 into a heat-exchanger 51 wherein it is heated and ultimately passes through line 56 into the upper portion of a. stripper 52. Chlorine is vaporized from the TiCl in the stripper 52 which is maintained at a temperature of C. to C. and a pressure of from 35 to 45 p.s.i.a. Separated chlorine gas is removed from stripper 52 through line 5 and introduced into the chlorination unit 1. The major portion of chlorine-stripped and heated liquid TiCL; is withdrawn through line 57 at the lower section of stripper 52 and is directed to heat-exchanger 51 through line 58 and finally returned to absorber 50 through lines 59 and 53. A minor portion of the chlorine-stripped liquid T iCl is returned to the stripper 52 through line 60, a boiler 61 and line 62. Sufficient heat is supplied to the returning liquid TiCl, by means of the boiler 61 in order to maintain the desired stripping temperatures.

I claim:

1. In a process for producing TiO from a titaniumcontaining material by chlorinating said material in a chlorination zone in the presence of a carbonaceous material to give an impure TiCl stream at least a portion of which is treated to give a pure TiCL; stream and oxidizing at least a portion of the pure TiCL; to give TiO and a chlorine containing off-gas which is passed to said chlorination zone, the improvement which comprises: selectively absorbing chlorine from part of said off-gas with TiCL; to obtain chlorine dissolved in TiCl recycling at least a portion of the chlorine dissolved in TiCL; to the chlorination zone, recovering the dissolved chlorine from the remainder of the TiCl, and recycling said recovered chlorine to said chlorination zone.

2. The process of claim 1 wherein the reaction temperature is maintained between about 950 C. and about 1050" C.

3. The process of claim 1 wherein the TiCl absorbent is obtained from the impure TiCl stream.

4. The process of claim 1 wherein the TiCl absorbent is obtained from the pure TiCl stream.

5. The process of claim 1 wherein the TiCl absorbent is obtained from both the pure and the impure streams.

6. The process of claim 1 wherein the reaction temperature is maintained between about 975 C. and about 1025 C.

References Cited UNITED STATES PATENTS 2,486,912 11/1949 Belchetz 23-87 2,675,891 4/1954 Frey 23-87 XR 2,701,180 2/1955 Krchma 23-87 2,758,019 8/1956 Daubenspeck et al. 23-87 XR 2,777,756 1/ 1957 Anazawa et al. 23-87 XR 2,792,077 5/ 1957 Mas et al. 23-87 XR 2,868,622 1/1959 Bennett et al. 23-87 3,120,427 2/ 1964 Mas et al 23-202 3,351,427 ll/1967 Wendell et al. 23-202 3,445,183 5/1969 Cairns 23-87 EDWARD STERN, Primary Examiner US. Cl. X.R. 23-87, 219 

